Vat dyestuffs and process of preparing them



Patented Nov. 21, 1933 were!) STA VAT DYESTUFFS AND PROCESS OF PRE-PARING THEM Wilhelm Eckert and Otto Braunsdorf, Frankforton-the-Main,Germany, assignors to General Aniline Works, Inc., New York, N. Y., acorporation of Delaware N Drawing. Application December, 5, 1930,

Serial No. 500,422, and in Germany December 9 Claims. (Cl. 260-44) Thisinvention relates to vat dyestuffs and a process of preparing them.

We have found that new valuable vat dyestufis are obtainable bycondensing naphthoylene-arylimidazol-peri-dicarboxylic acid or aderivative of this compound of the following general formula:

/R a E 0c 0 Hood coon wherein R, represents an arylene group,'bound inBoth processes are to be regarded as equivalent 'and they are bothenclosed in the present invention and in the claims.

The vat dyestuffs thus obtainable correspond with the following generalformula:

wherein R1 stands for an arylene group, bound tuted,. R2 stands for,hydrogen, an alkyl-., aryl'-, aralkylor a hydrogenated aryl-group oranamino group which may be substituted by a phenyl group and Vwherein'thenaphthalene-nu eleusmay besubstituted, for instance,-by haloin twoadjacent positions, which may be substi gen, It is a'surprising factthat the new derivatives are useful vat dyestuffs since the 1.4.5.8-naphthalene-tetra-carboxylic acid di-alkyl-or arylimides of thefollowing formula:

r 3 N Iv oo oo are nearly colorless. n

The new dyestufis are distinguished by their clear tints, great dyeingpower and good fastness properties. r The same dyestuffsmay be obtainedby condensing a naphthalene+tetra-carboxylic acid derivative of one ofthe general formulae:

foi 7 o l .Rm.

wherein R stands for hydrogen,v an alkyl-,aryl-,

aralkyl-"or a hydrogenated aryl-group or a sub stituted= orunsubstituted amino group such, for instance, as hydrazine, with anortho-diamme or.

a salt thereof in the absence or in the presence of a solvent or adiluent.

The same dyestuffs are likewise obtained by condensing the abovementioned parent material with an ortho-nitro-amino compound andtreating the condensation products which correspond with the followingformula:

Co a

sets in with elimination of water. After heating for some hours, thesolution is diluted with ethyl alcohol, filtered with suction and thesolid matter is washed first with alcohol and then with dilute sodiumcarbonate solution and finally with water. The dyestuff thus obtained isa microcrystalline yellow powder which dissolves in concentratedsulfuric acid to a yellow solution. It dyes cotton from a redhydrosulfite Vat reddish yellow tints of good fastness to chlorine.

(2) 1 part of naphthoylene-benzirnidazol-peridicarboxylic acid or of theanhydride thereof is heated with 2 parts of beta-naphthylarnine in 20parts of trichlorobenzene to temperatures in the neighborhood of 200 C.until any unacted upon parent material can no longer be detected. Aftercooling, the solution is filtered with suction, the solid matter isfreed from an excess of beta-naphthylamine and the solvent by means ofalcohol. The condensation product of the following formula:

is obtained in the form of a yellow powder which dissolves inconcentrated sulfuric acid to a yellow solution and dyes cotton from ared alkaline melt is heated for several hours to about 180 C.-

200 C. while stirring. After cooling, the crystalline reaction productwhich has been formed,

i. e. the parachloranilide ofnaphthoylene-benzimidazol-peri-dicarboxylic acid of the formula:.

is separated from the excess of para-chloraniline by treating thesolidified melt with a suitable solvent such, for instance, as alcohol.stuff is obtained in the form of reddish prismatic small crystals which,when heated to 370 0., remain entirely unchanged. It dissolves insulfuric acid to a yellow solution. From a red hydrosulfite vat it dyescotton yellow tints.

(4) 3.4 parts of naphthoylene-benzimidazolperi-dicarboxylic acid or ofthe anhydride thereof are heated with 15 parts of para-xylidine to about200 C. for about 5 hours. The melt is worked upas described in thepreceding exam- The dyepoint of the base.

to: vi

"ples and yields' a dyestuff which corresponds with 'the probableformula: j 3 I It is obtained in the form of microcrystalline feltedyellow small needles; it dissolves in concentrated sulfuric acid to ayellow solution and dyes cotton from a red hydrosulfite vat yellowtintsf. v 1. l

(5) By using in Example 4 instead of "para- Xylidine the correspondingquantity of asymmet rical metwxylidine, there is obtained a verysimilaryellow dyestufi having, propertiessimilar to those of theisomerides.

(6) 1.5 parts of naphthoylene-benzimidazolperi-dicarboxylic'acidanhydride are heated-with 8-10 pa'r'ts'oi ortho-toluidine near to' theboiling acetate may be added; When any unchanged parent material can nolonger be detected,- thesolution is filtered with suction,v thes olidmatter is'washed with alcohol andwater. The dry 'cona densation product,probably-the orthoetoluidide of naphthoylene-benzimidazol peridicarboxylic 3 acid which corresponds with the following probableformula: V

is a brownish yellow amorphous powder. It dissolves in concentratedsulfuric acid to a yellow solution and dyes cotton from a red vatyellowish tints.

(7) 3.4 parts of naphthoylene-benzimidazolperi-dicarboxylic acidanhydride' are heated to boiling for some hours" under reflux with 5-6times their weight of cyclohexylamine or a larger In order to promotethe con-v densation'a small quantity of'dehydrated sodium.

excess of an aqueous solution of cyclohexylamine ofabout'50% strength.Thewhole is thenfdiluted with water and the dyestuff which has'separatedin small orange crystalline needles is fildissolves concentratedsulfuric acid to a yellow solution and dyes cotton from a dark redalkaline hydrosulfite vat clear reddish yellow tints oflgood fastnessproperties.

(8) '1.75 parts of naphthoylenemethyl-benzimidazolperi-dicarboxylic acidanhydride are introducediijnto 6 partsof molten para-toluidine and themelt is heatedfor some time near to the boiling point of theparaet'oluidine. When the cold melt is worked up with alcohol and waterthe condensation product is obtained in the form of an orangelresiclue.It dissolveain concentrated' sulfuric'facid to a reddish yellowsolution: It

dyes c'ottonfromadark red alkaline hydrosulfite vat, w hichisformedeasily and quickly even at ordinary temperaturareddish yellowtints. T he dyestuff most probably oorresponds'with the followingfqimulaz "(9)" l-mart'of na'phthoylene-benzimida2ol peridicarboxylioaoid-anhydride is inix'ed' withb parts of'beta-hydr0xy-eth3ilaniine andthe mixture is slowly heated. Temporarily the anhydride dissolves-butsubsequently the mixture solidifies on" further heating with eliminationof small micro crystalline needles? After-the reaction is complete, thewhole is diluted withwater, filtered with 25k and dyes cotton from a redhydrosulfite vat yelsuction; the'solid matter is washed with waterand'dried. The reaction product which probably is thebeta-hydroxy-ethylimide of thenaphthoylene-benzimidazol-peri-dicarboxylic acid and corresponds withthe following formula:

OH forms an orange crystalline powder; it dissolves in concentratedsulfuric acid to a yellow solution V peri-dicarboxylic acid anhydrideand 15 parts of hydrazine hydrate are warmed together. The anhydridegradually dissolves whereby the solution slowly becomes dark red. Whenthe solution has assumed its reddish coloration, it is dilutedwith waterwhereby a clear red solution of the leuco compound of the condensationproduct,

formed by the reducing action of'the hydrazine, is obtained. By blowinga current of air through the solution an orange precipitate is obtained.It is filtered with suction, washed with water and may be directly used,in the form of ap'aste, for

dyeing purposes. It dyes cotton from a red hydrosulfite vat, which iseasily formed even in the cold, reddish yellow tints and has thefollowing *probable constitution: i

0 I THa (12) 4.1 parts of naphthoylene-4.5-dichl0robenzimidazol-peri-dicarboxylic acid or the corresponding quantity of theanhydride thereof are heated to gentle boiling for some hours with 5-6times their weight of cyclohexylamine.

After cooling, the solution is filtered with suction, the solid matteris washed with cyclohexylamine and hot water. The dyestuff is a yellowpowder and dyes cotton from a green weakly alkaline hydrosulfite vatyellow tints of good fastness properties. The dyestuff corresponds withthe following probable formula:

(13) By using instead of thenaphthoylene-4.5-dichlorobenzimidazol-peri-dicarboxylic acid the correspondingquantity of naphthoylenechloro bromo benzimidazol-peri dicarboxylic acida dyestuff is obtained which hardly differs in its properties from thoseof the dyestufi obtainable according to Example 12.

' (H) By causing naphthoylene-dichloro-benzimidazol-peri-dicarboxylicacid anhydrideobtain'able for instance, by condensingacenaphthene-4.5-dicarb'oxylic acid with 3.5-dichloro-1.2-diaminobenzene and oxidizing the benzimidazol derivative thus obtainedtoreact with cyclohexylamine a dyestuff is obtained which dyes cotton froma feebly alkaline hydrosulfite vat clear reddish yellow tints of goodfastness properties.

(15) By condensing acenaphthalic acid with3.5-dibromo-1.2-diaminobenzene and oxidizing this condensation product,naphthoylene-dibromo-benzimidazol-peri-dicarboxylic acid is obtainedwhich on reaction with cyclohexylamine yields a yellow dyestuff ofproperties very similar to those of the dyestufi described in Example14.

(16) 4 parts of naphthoylene-benzimidazolperi-dicarboxylic acidanhydride and 10 parts of benzylamine are heated together to about 150C.- 160 C. for some hours. The dyestufl which prob ably has theconstitution of a benzylimide of naphthoylene benzimidazol peridicarboxylic acid thereby precipitates in the form of reddish yellowcrystals. After cooling, it is filtered with suction, washedwith alcoholand hot water and dried. It forms a reddish yellow powder and dyescotton from a red feebly alkaline hydrosulfite vat clear redish yellowtints;

(17) 10 parts of 1-4-5-8-naphthalene-tetracarboxylic acidmonophenylimide are heated to boiling for about halfan hour with 4 partsof ortho-pheylenediamine in 100 parts by volume of glacial acetic acid.After-cooling, the dyestufi which has been formed, is filtered withsuction, washed with water and dried. It crystallizes in the form ofyellow laminae and dissolves in concentrated sulfuric acid to a yellowsolution. It dyes the vegetable fiber from a red vat reddish yellowtints and has the following constitution;

(18) By using in Example 17 instead of orthophenylene-diamine orthonitraniline and heating "to gentle boiling for some time 10 parts of thecondensation product in about 200 parts by volume of glacial acetic acidin the presenceof anexcess of pulverized iron, a dyestufi of the sameconstitution as described in Example 17 separates.

(19) 20 parts of 14'5-8-naphthalene-tetra-carboxylic acidmono-beta-naphthylamide of the following'formula: 4

presence of an inert diluent.

5 (20) :Byusing in Example 1? instead of orthophenylenediamine,ii-vmethyl-1.2-diaminobenzene and proceeding as indicated in thatexample, a dyestuff of the following constitution:

n 7 CH: v is obtained having properties similar to those of the productof Example 17.

We claim: v 5 1. The process which comprises condensing a compound ofthe followinggeneral formula N N oo o no Hood (1003' wherein Rrepresents an arylene of the. group consisting of phenylene,methylphenylene, halogenphenylene and naphthylene, bound'in two ad-1jacent positions, with acompoundof the general formula X-NH2 wherein-X1represents a radical of thegroupconsisting of hydrogen, hydroxy-vphenyl, halogenphenyl, methylphenyl,

naphthyl, cycloheXylQamino and phenylimino, by

. heating the compounds in the presence of an inert diluent. t-

2. The process which comprises condensing a compound 01 the followinggeneral formula Hoot, 'oooi-r V wherein R represents an arylene ofthegroup consisting of phenylene, methylphenylene, halogenphenylene andnaphthylene, bound in two adjacent positions, with a compound of thegeneral formula X-NI-Iz wherein X represents a radical of the groupconsisting of hydroxyethyl,

phenyl, halogenphenyl, methylphenyl, cyclohexyl and amino, by heatingthe compounds in the 3. The process which comprises'oondensing acompound of the following general formula R so OCAO/ OG\N/CO 5 l 1 r IH0O 00011 I R2 wherein R1 represents a=phenylene group, bound 9D in twoadjacent positions, which may be substituted by halogen or methyl and R2represents a radical of the group consisting of hydroxyethyl; phenyl,halogenphenyl, methylphenyl, cyclohexyl and amino said compoundsrepresenting useful vat dyestuffs of clear tints, strong coloring powerand good fastness properties.

7. As a new product, the compound of the following formula wherein Rrepresents a phenylene group, bound in two adjacent positions, which maybe substituted by halogen or methyl with a compound of the generalformula X--NH2 wherein X represents a radical of the group consisting ofhydroxyethyl, phenyl, halogenphenyl, methylphenyl, cyclohexyl and amino,by heating the compounds in the presence of an excess of the saidcompound of the formula X-1 TH2.

4. The process which comprises condensing naphthoylene 4.5dichloro-benzimidazol-peri dicarboxylic acid of the following formula0.3% OO V/ nooo OOH v p with cyclohexylamine by heating the compoundsCH2 in the presence of an excess of boiling cyclo- I 20 CH CHhexylamine. l 5. As new products, the compounds of the fol- CH2 lowinggeneral formula: being a yellow powder and dyeing cotton from a greenfeebly alkaline hydrosulfite vat yellow tints R1 of good fastnessproperties. 25 8. As a new product, the compound of the fol- A lowingprobable formula Br Br W 13s Br I L N /N 0 co or. on;

wherein R1 represents an arylene of the group consisting of phenylene,methylphenylene, halo- -2 genphenylene and naphthylene, bound in twoadjacent positions, and R2 represents a radical of V l the groupconsisting of hydrogen, hydroxyethyl, 0o 00 00 v 00 phenyl,halogenphenyl, methylphenyl, naphthyl, or cyclohexyl, amino andphenylimino, said coml l pounds representing useful vat dyestuifs ofclear 3 tints, strong coloring power and good fastness 1120 OH: H26 0115properties. I l I '6. As new products, the compounds of the fol- H2O CH2H20 CH2 lowing general formula fi, 6

being a yellow and powder and dyeing cotton from a feebly alkalinehydrosulfite vat clear reddish-yellow tints of good fastness properties.

9. As a new product, the compound of the 01- lowing probable formula ocs forming reddish prismatic crystals which do not change when heated to370 0., dissolving in sulfuric acid to a yellow solution and dyeingcotton from a, red hydrosulfite vat yellow tints.

WILHELM ECKERT. OTTO BRAUNSDORF.

